JPS5929243A - Photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive silver halide material with high sensitivity and superior stability to aging by forming an emulsion layer contg. silver halide particles having crystal faces with specified Miller indices in a specified areal ratio on a support. CONSTITUTION:At least one silver halide emulsion layer is formed on a support. The layer contains simply dispersed silver halide particles, and the outer surfaces of >=50% of the silver halide particles have crystal with Miller indices (100) and (111). The real ratio between the (100) and (111) faces satisfies the equation [where K is the ratio between the intensities of diffracted rays belonging to (200) and (222) faces measured by an X-ray diffraction analysis method].

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the improvement of photographic materials using Rogonized Saba 4Ji4, more specifically, Rogonized mackerel 4Ji4, which has high sensitivity and excellent stability over time as an emulsion coating solution and a photosensitive material. Related to silver photographic materials.

In recent years, with the advancement of photography technology, cameras have been made smaller and lighter, and in response to the growing demand for something that is easy to take pictures with and that does not fail, we have developed silver oxide photosensitive lenses for photography. Materials are also required to have higher performance, for example, there is a strong demand for the development of silver rokenide photographic materials that have high sensitivity, excellent sharpness and graininess, and have a wide exposure latitude.

Regarding the improvement of the photographic performance of the above-mentioned silver rognide photographic light-sensitive materials, ``CU'', for example... silver rognide grains have a nearly uniform shape, a narrow particle size distribution, and a low quantum efficiency due to It has been proposed to use a monodispersed emulsion which has improved sensitization efficiency.

In addition, the use of this monodisperse emulsion can achieve high sensitivity without increasing fog, which has been in particular demand in recent years, and can also be applied to the development of silver-logonide photographic materials with a low silver content. It is also something that has received a lot of attention.

In this way, monodispersed emulsions are emulsions with excellent sensitization efficiency that can uniformly impart chemical sensitization nuclei to the valleys and silver lokenide grains during chemical ripening, but they do have problems with image tone (tonality). )
It has the disadvantage that it becomes hard and the exposure latitude becomes narrow. In addition, depending on the shape of the particles, the sensitizing nuclei of the above-mentioned chemical sensitizing nuclei are likely to be formed in the silver oxide, which lowers the sensitizing efficiency and also has poor adsorption of sensitizing dyes. In some photosensitive materials, there is a strong tendency for dye desorption to occur during the manufacturing process, resulting in desensitization. Furthermore, monodispersed emulsions with different particle shapes have poor storage stability;
For example, fog not only occurs during the chemical ripening process, but also after the chemical ripening process, during the manufacturing process of silver halide photographic materials, or when storing silver halide photographic materials over time. There is a drawback.

In order to improve the image quality of silver halide photographic light-sensitive materials, one of the techniques for improving image characteristics such as gradation, graininess, or sharpness is to improve the silver halide composition, especially It is a well-known technique to improve image quality by changing the amount of silver iodide in silver iodobromide and utilizing the development suppressing effect of iodide ions released during development. However, increasing the content of silver iodide in this way
Although silver iodide is preferable as a means for improving image quality, on the other hand, it is not necessary for improving sensitivity because silver iodide acts as a suppressor during sulfur sensitization during chemical ripening or against the monochrome effect. It cannot be said that it is a preferable method.

The desensitization caused by the inhibitory effect that occurs during chemical ripening or development can be considerably recovered by, for example, not adding increased amounts of sulfur sensitizers, gold sensitizers, etc. during chemical ripening, or can be improved at the same time. The disadvantage is that the application of a detergent deteriorates the stability of the photosensitive material over time, making it more likely to cause fogging.

Therefore, the purpose of Fu2amei is to provide a silver parokenide photographic light-sensitive material with a fog of 1. The object of the present invention is to provide a silver oxide photographic material that has excellent storage stability over time.

As a result of various studies conducted by the inventors regarding the above-mentioned problems, the silver halide emulsion layer in silver halide photographic photosensitive material 1, which has at least one 710 silver saponide emulsion layer on the support, has been found to be At least one layer of the layer contains monodisperse silver chloride grains, and the silver halogenide emulsion layer contains at least 50% of the silver chloride grains. The surface is mirror finger gauze (100') and I 1
11), and the (10θ) plane and (
The surface area ratio of the 111) planes satisfies the following relational expression (11) by 1σ.It has been found that the above object can be achieved by using a silver rokenide photographic light-sensitive material.

Relational expression (1) Here, the ratio of the intensity of each diffraction line attributed to the <200) plane and the <222) plane measured in the K1-j-X-ray diffraction analysis method, that is, the (222) plane It is expressed as the diffraction ff# intensity attributable to .

The present invention will be explained in more detail below.

In the present invention, monodisperse silver halogenide grains are those in which, when an emulsion is observed using an electron micrograph, the shape of each silver halogenide grain appears uniform and the grain size is uniform.
And it has a particle size distribution as defined by the following formula. That is, when the standard deviation S of the particle size distribution is divided by the average particle size A, the value is 20 or less.

Σnl −≦0.20 The average grain size here refers to the diameter of a spherical silver lognide grain, or the projected image of a grain of a shape other than a cube or sphere to a circle of the same area. It is the average value of the diameter when converted to 1, where the individual particle size is rl and the number is nI, and r is defined by the following formula.

The above particle size can be measured by various methods commonly used in the technical field for the above purpose. Typical methods and 17 include Loveland's 1 particle size analysis method JA, S.

'l'', M, Symposicum Fist-On-Meet-It φ Microscopy, 1955, pp. 94-122 f or [Photo)° Theory of Processes Co-authored by J Mies and James, No. 3
This particle diameter can be measured by dividing the projected area of the particle by 1 to an approximate value of the diameter.

If the particles have a substantially uniform shape, the particle size distribution can be determined by the diameter or projection surface A factor! 71 I can definitely wear this.

The relationship between grain size distribution is [Empirical relationship between centometric distribution and grain size distribution in photographic emulsions] The Journal of Photography, Vol. LXXIX, (1949)
This can be determined using the method described in the paper by Triheli and Smith.

The silver halide grains used in the silver halide photographic light-sensitive material according to the present invention contain monodispersed silver halide grains according to the present invention that account for at least 75% of the total grains in the halofluoride emulsion layer. It is preferable that the particles are crushed, and it is particularly desirable that all the particles are particles of the same size.

In addition, the soil that controls the gradation is used to mark the non-invention.
It may contain one Halokunite particle other than the Haloke/Kahan particle. 1 Furthermore, in the silver halide grains according to the present invention, 50% or more of all the grains in the same silver halide emulsion layer are halide grains that cure crystal planes that satisfy the relationship shown below. .

Regarding the definition of the surface of silver halide grains in non-invention, for example, as described in "Bulletin of the Society of Photography of Japan" Section 13, Section 5. It is defined as follows based on the 4ir diagram obtained from the powder method xH batch analysis of an emulsion containing silver halide grains oriented to the substrate beads and enriched.

That is, in the Xi batch analysis, the X axis is CL)-K
Using the a-line, if the (200) plane corresponds to the (1oo) plane of the silver halide grain, then the (200) plane corresponds to the (111) plane of the silver halide grain.
222 ) plane diffraction @ (respectively Im angle of analysis (2e ) 75E approx. 3 (1,9° U 55.oo
K KM will pass. ) and take their ratio.The intensity ratio of the above two types of diffraction lines for the black crystal, that is, expressed as K = 100/
The latter octahedral crystal with 0-fold alignment is expressed by K = 0/100.

Therefore, according to the above method, preferred silver halide grains u 100 / 13≦IC≦l0ft1 in the present invention
The vomit dispersion falls within the range of 0.2... It is a lokenized emulsion.

In the silver roganide photographic light-sensitive material of the present invention,
The silver halide grains contained in the silver halide emulsion layer contain silver iodide, and the proportion of silver iodide in the silver halide is 3 to 12 mol%, preferably 5 to 10 mol. %
The use of particles is suitable for achieving the purpose of the present invention. Also, silver iodide other than the above-mentioned silver iodide may be used.

Further, the silver halide grains according to the present invention are preferably so-called core-shell type silver halide grains. The core-shell type silver halide grains according to the present invention consist of a core made of silver halide containing silver iodide, and a shell made of silver halide containing silver iodide, and a shell made of silver halide containing silver iodide. Saga(1,0(11~0.
The silver halide grains are 1p.

In a preferred embodiment of the present invention, the silver halide composition of the core is 3 silver iodide.
In yet another preferred embodiment of the present invention, the core contains silver rognide, and the shell contains 0 to 6 mol% of silver iodide. The silver halide grains are monodisperse, and the shell thickness is 0.002 to 0.08 μm.

The silver halide emulsion of the present invention having silver halide grains having a specific thickness σ5 shell is produced by coating the core with silver halide grains contained in a monodisperse emulsion with a shell. can do.

To make the core a monodisperse silver halide grain, PA,!
Particles of a desired size can be obtained by the double die method while keeping / constant. Also book 48fi21
The method described in Publication No. 1 can be applied. For example, it is produced by adding a potassium iodobromide-ceratin aqueous solution and an ammoniacal silver nitrate aqueous solution to an aqueous gelatin solution containing silver rognide seed particles while changing the addition rate as a function of time. At this time, by appropriately selecting the time function of the addition rate, pH, pAg, temperature, etc., it is possible to obtain a highly monodisperse silver oxide emulsion.

Next, the thickness of the shell that covers the core must be thick enough not to hide the desirable qualities of the core, but also thick enough to hide the unfavorable qualities of the core.1. That is, the thickness is limited to a narrow range defined by such upper and lower limits. Such a shellfish can be formed by depositing a soluble halogen compound solution and a lubricating silver salt solution on a medium-disperse core by the double jet method.

As described in detail above, the silver rokenide photosensitive material of the present invention contains a monodisperse emulsion in which silver rognide grains have a crystal structure as defined by the above relational formula (11). Decrease in sensitizing efficiency, desorption of sensitizing dyes, increase in fog, and deterioration in storage stability over time when grains of conventional monodisperse emulsions are made of octahedral, tetradecahedral, or cubic crystals. As a result, the sensitization efficiency was significantly increased without fogging, and the exposure latitude was also improved.

The above effects according to the present invention were achieved by monodisperse silver halide grains having crystal structures as defined in the present invention. Further, the effect is more pronounced by adjusting the silver iodide content of the silver halide grains as described above and by making the grain structure into a core-shell type.

Further, in the present invention, the chemical sensitization effect of the silver halide grains according to the present invention can be significantly enhanced by chemical ripening in the presence of a silver halide bath agent.

Examples of silver halide solvents used in the present invention include U.S. Pat. No. 3,271,157, U.S. Pat. fa) organic thioethers described in JP-A No. 54-1fi8917, etc., JP-A-53-82408, JP-A No. 55-
No. 77737, No. 55-2982, etc. (b
) Thiourea derivatives, described in JP-A-53-144319 (c) Silver halide solvents having a 5M acid or a thiocarbonyl group sandwiched between a sulfur atom and a nitrogen atom, JP-A-54- Examples include (d) imidazoles, (e) sulfites, and (f) thiocyanates described in No. 100717.

Specific examples of these compounds are shown below.

(al HO-(CH2), 8-(OH,)t-s-(OH,)
, -0H12-NHeOOH,0H2000H 0H2-8-0 Horse OH2S C,H,l(b) (fJ N H4S ON

The amount of the solvent used in the present invention varies depending on the type of solvent and other factors, but for example, in the case of thiocyanate, i is preferably in the range of 5 to 11 parts per mole of silver chloride.

The silver halide grains according to the present invention can be subjected to various commonly used chemical sensitization methods. That is, oil-based seratin: water-soluble gold salt, water-soluble platinum salt, water-soluble palladium salt,
Noble metal sensitizers such as water-soluble rhodium salts and water-soluble iridium salts; sulfur sensitizers; selenium sensitizers; polyamines, styl chloride
Chemical sensitization can be carried out using a chemical sensitizer such as a reduction sensitizer such as tin or the like, either alone or in combination.

In the present invention, it is preferable to coexist the silver halide solvent during the chemical sensitization.

Emulsions containing silver halide grains according to the invention can be optically sensitized to a desired wavelength range. The method for optically sensitizing the silver halide emulsion according to the present invention is not particularly limited. It can be optically sensitized (e.g. superchromatic sensitization). These techniques are described in U.S. Pat. Nos. 2,688,545 and 2.
No. 912,329, No. 3,397,060, No. 3
．． 615,635, British Patent No. 3,628,964, British Patent No. 1,195,302, British Patent No. 1,242,588
No. 1,293,862, West German License No. (oLS)
It is also described in Japanese Patent Publication No. 2030.325, No. 2,121,780, Japanese Patent Publication No. 43-4936, No. 44-14030, etc. The selection can be arbitrarily determined depending on the purpose and use of the silver halide photographic material, such as the wavelength range to be sensitized and sensitivity.

The monodisperse silver halide emulsion according to the present invention can be used as is with its grain size distribution, or monodisperse silver halide emulsions with different average grain sizes of 2 m or more can be blended at any time after grain formation. It may be used after being mixed to obtain a predetermined gradation. But that t? ! , or those containing silver halide grains other than those of the present invention to the extent that the effects of the present invention are not impaired.

The silver halide emulsion according to the present invention can contain various commonly used additives depending on the purpose. Examples of these additives include stabilizers and antifoggants such as azaindenes, triazoles, tetrazoles, imidazoliwam salts, tetrazolium salts, and polyhydroxy compounds;
Aldehyde type.

Aziridine series, inoxazole series, vinyl sulfone series, acryloyl series, albodiimide series, maleimide series,
Hardeners such as methanesulfonic acid esters and triazine thread; Development accelerators such as benzyl alcohol and polyoxyethylene compounds; Image stabilizers such as Chroman, Claman, bisphenol and phosphite esters; Wax, high grade Examples include lubricants such as glycerides of fatty acids and higher alcohol esters of higher fatty acids. In addition, as a surfactant, it can be used as a cleaning aid, a permeability improver for processing liquids, an antifoaming agent, and as a floor material for controlling the physical properties of photosensitive materials. Various nonionic or amphoteric types can be used. As antistatic agents, diacetylcellulose, styrene barfluoroalkyl lysium maleate copolymer, styrene-
An alkali salt of a reaction product of maleic anhydride copolymer and p-aminebenzenesulfonic acid is effective. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. It is also possible to use colloidal silicon oxide. Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, and other monomers having ethylene groups. Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate copolymers, alkyl vinyl ether-maleic acid copolymers, and the like.

Supports for silver halide photographic materials prepared using the silver halide emulsion according to the present invention prepared as described above include, for example, writer paper, polyethylene-coated paper, polypropylene/synthetic paper. , glass paper, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, polystyrene, etc.
Each of these supporting materials is appropriately selected depending on the purpose of use of the silver nitride photographic light-sensitive material.

These supports are subjected to undercoat processing, if necessary.

The silver halide emulsion according to the present invention has a wide variety of uses (7) such as black and white general use, X-ray use, color use, infrared use, micro use, silver dye whitening method, reversal use, and diffusion transfer method use. It can be effectively applied to photosensitive materials.

Also, due to an uninvented invention... Silver Lokenide emulsion was used for color...
To apply to silver halide photographic light-sensitive materials, cyan, cyan,
It is sufficient to apply a method and cable barrel used in color photolithography, such as containing a combination of magenta and yellow couplers, and a known open-chain ketomethylene coupler can be used as the yellow coupler. Among these, benzoylacetanilide and pinochoylacetanilide compounds are useful.

Magenta couplers include pyrazolone compounds, indacylon compounds, and cyanoacetyl compounds, and cyan couplers include phenolic compounds and naphthol yarns.
Compounds etc. can be used.

When the silver rognide emulsion containing silver rognide grains according to the present invention is used in a silver rokenide color IC photoreceptor as described above, for example, in a multilayer silver rokenide color IC photoreceptor. may be applied to the photosensitive "Il agent layer" of gold dust, but it is preferably applied to at least the green-sensitive silver/rokenide emulsion layer.

In addition, when the roggonized steel emulsion layer having the same color sensitivity is composed of two or more layers having different photosensitivity, it is preferable to apply the method to the silver halide emulsion layer having the lowest photosensitivity.

+: Silver halide photographic materials and materials prepared using the silver halide emulsion according to the invention can be developed by a commonly used known method after exposure.

The black and white developer is an alkaline solution containing developing agents such as hydroxybenzeas, amine phenols, and aminopene monos, as well as sulfites, carbonates, and other alkali metal salts.
It can contain bisulfites, bromides, iodides, etc.

In addition, when the silver halide photographic light-sensitive material is for color use, color development can be carried out by a commonly used color development method.In the reversal method, it is first developed with a black and white negative developer, and then white lightning is applied. Alternatively, the film is treated with a bath containing a fogging agent, and further color-developed with an alkaline developer containing a color-developing IW agent. There are no particular restrictions on the processing method, and any processing method can be applied. For example, a typical method is to perform Ti color development, then standard H constant layer processing, and further wash with water and anti-oxidant treatment as necessary. Alternatively, after color development, a method can be applied in which treatment and whitening are carried out separately, and if necessary, the spatula is washed with water and treated with water.

Next, the non-invention will be specifically explained with reference to Examples, but the non-invention is not limited to these.

Example 1 Polydispersity (dispersity 8/〒=(
1,34) twin emulsion (referred to as emulsion A), monodisperse emulsion of octahedral crystals (S/〒=0.10) (referred to as emulsion B), monodisperse emulsion of cubic crystals (referred to as S/lower -0, 10) Emulsion (referred to as emulsion C) and qt derivation of three types of tetradecahedral crystals with different ratios of (100) and (111) planes (S/i ne=
0.10) Emulsion (emulsion of these.

(referred to as E and P') were prepared, respectively. (See Table 1.) - To each of the above emulsions, add sodium thiosulfate, chloroauric acid, thiona7rlI'a/monium, and the sensitizing dyes listed in Chemical sensitization and spectral sensitization were performed under the following conditions.

7J of the following stabilizer was added to each emulsion obtained by the two sets.
Some of the samples were treated immediately, and the remaining samples were kept at 40°C for 6 hours before adding a hardener and a φS fabric aid, which are commonly used in the production of color coupler dispersions. 'Coated on an acetate film-based support and dried.

[L Sokan Pigment]

[Stabilizer] (a) 4-Hydroxy-6-medyru 1.3.3a.

7-tetodizainthene (b)]-phenyl-5-mercapto-tetrazole [color coupler] 1-(2,4,6-drichlorophenyl)-nee 1-C
Sensitometry of each of these samples was carried out by the following method.

As a light source for exposure, a tungsten bulb (color part II 5
, 4oo0K) for 1150 seconds of exposure through a filter and an optical wedge. Next, color development was carried out at 38° C. for 2 minutes and 45 seconds using a color developer having the following composition.

[Color development surface composition]

Potassium bromide 1.16,!
i' Sodium chloride 0.14.
9 Nitrilotrivine vinegar jV2 competition: trisodium salt (monohydrate) 1.20. 9
Water to potassium chloride 1.48,
! ? Add water for 0 days] and set it as e.

The sensitometry results are shown in Table 1 below.

Note that the sensitivity is expressed relative to the sensitivity of Emulsion A as 100.

(Table 1) From the results in Table 1 above, it can be seen that the Rogun silver emulsion and E related to the present invention are samples coated not only immediately after ripening but also after 6 hours, and Kaeshima wear is a sample coated over time along the emulsion. It was revealed that there were few changes, low capri, and high sensitivity.

Next, the stability against heat of the above-mentioned sample coated on studs at the end of ripening l' was investigated, and the results are shown in Table F.

(Table 2) From the above results, it can be seen that the emulsion (material and E
When preserving the o-plane part F, the sensitivity and fog ratio is 1!
T! It was found to be stable.

Example 2 In the same manner as in Example 1, five types of dodecahedral crystals with an average grain size of 0.46 tt were prepared using iodide-containing leaves or x 14 diffraction bamboo according to the table: Core-shell type annual dispersion silver iodobromide agent (core is silver iodobromide, S/
〒=(1,1”2, shell is nicked silver, shell thickness is L)
(14a)) iA iα and emulsion G
,H.

I, J, Nitoshi. Separately from these, a monodispersed emulsion of dodecahedral crystals in which there is no 171 ruyl and iodine is evenly distributed throughout the silver grains was prepared, and this was emulsified and designated as M.

Chemical sensitization and spectral sensitization were carried out by adding sodium thiosulfate, chloroauric acid, ammonium thiocyanate, and the following sensitizing dyes to each of the above emulsions so that the gradations of each emulsion were approximately equal.

To each emulsion obtained above, the same stabilizer as in Example 1, the following color coupler dispersion layer, a commonly used hardener and coating aid were added, and the mixture was coated and dried on a triacetate film base support. I let it happen.

[Sensitizing dye]

[Kafura] 1- Pidroki 7-2- [δ-(2I4-Gi-mo-1')
[milquenoquine]-n-butyl]naphthamide Each of the above samples was prepared and treated in the same manner as ill, and sentimetry was performed. So σ) The result is FFi self σ) Third
71< on the table.

Silver oxide emulsions were prepared (emulsions A, B, and C). The respective silver iodide contents were 4 mol, 6 mol, and 8 mol%, and the X-ray diffraction peak ratios (K) were +110/4.24 and 100/
It was 2.10°10o/1.50, which was within the specified range of the present invention.

These emulsions A, B, and C were used as real 71iSi example 1,
Chemical sensitization and spectral sensitization were carried out in the same manner as 2° and 3.
The emulsions were made into red-sensitive, green-sensitive, and ■-sensitive emulsions.

A normal multilayer color negative film was made using these emulsions and a heat resistance test was conducted, but Table F shows that, as in Examples 1 and 2, there was little change in magnetic waves and fog in each photosensitive layer. It was confirmed that there was.

(Table 5) Agent: Yoshi Kuwahara Written amendment to the proceedings, arrived at the Commissioner of the Patent Office on November 1980, Mr. Kazuo Sugi. Display of the case: 1982 Patent Application No. 139561-1j2, Name of invention: Silver halide photograph Photosensitive Material 3 Relationship with the Fixer Nail Case Patent Applicant Address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (+27) Konishiroku Photo Industry Co., Ltd. Ne1 For Representative Director
Moto Nobuhiko 5, Date of amendment order + 1 Voluntary action 6, IIYI of “Feature 1 “F claims” of the specification subject to amendment and Plate 7 of “0 and K (11 explanations of the invention”), Supplement Contents of Section 3 (1) The scope of the claims shall be amended as shown in the attached sheet.

(2) The detailed description of the invention is amended as follows.

Attachment 2. A silver halide photographic material having at least one 710 silver emulsion layer on a support, at least one of the silver halide emulsion layers containing monodisperse silver halide grains, and The outer surfaces of 50% or more of the silver halide grains contained in the silver halide emulsion layer have crystal planes with Miller indices (100) and (111), and the (100) plane and A silver halide photographic material characterized in that the area ratio of the (111,) plane satisfies the following relational expression (I).

Relational expression (11 [where ■( is measured in X-ray diffraction analysis method)
(200) and (222) planes, respectively.
00) diffraction line i! It is expressed as i1 degrees. ]

Claims (1)

[Scope of Claims] A silver rognide photographic light-sensitive material having at least one layer of silver rognide emulsion on a support;
At least one layer of the silver rokenide emulsion layer contains monodisperse silver oxide grains, and contains at least % of the silver oxide grains contained in the silver rokenide emulsion layer. The outer surface of the silver oxide grain has a Miller index of (100) and (11
1), and the (lOO) plane and the (1)
11) A silver rokenide photographic material, characterized in that the area ratio of the surfaces satisfies the following relational expression (1). Relational expression (11 [Here, K is measured by X-ray diffraction analysis method (2
It is expressed as the ratio of the intensities of the diffraction lines belonging to the (200) plane and the (200) plane, that is, the intensity of the diffraction lines belonging to the (200) plane. ]